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The hydrogen atom

Chap. 9

unr , l (r) G pnr , l (r)X By combining these three characteristics, we arrive at a radial eigenfunction of the form unr , l (r) Npnr , l (r)rl1 erana0 , (9X24)

where N is a constant which ensures that the normalization condition (9.12) is satisfied. Explicit expressions for the radial eigenfunctions with low values for the angular momentum quantum number l and low values for the radial quantum number nr are given in Table 9.1, and some of these eigenfunctions are illustrated in Fig. 9.4. To conform with the conventions of atomic physics these eigenfunctions are labelled using spectroscopic notation. This notation employs the principal quantum number n nr l 1 and a letter to designate the value of l; the letter s is used for l 0, p for l 1, d for l 2, and f for l 3. The historical origin of this notation dates back to the early days of atomic physics when spectral lines were labelled s for sharp, p for principal, d for diffuse and f for fundamental.
TABLE 9.1 atom Spectroscopic notation 1s 2s 3s 4s 2p 3p 4p 3d 4d Normalized radial eigenfunctions for low-lying states of the hydrogen

Radial eigenfunction unr , l (r)   2 r raa0 u0, 0 (r) p e a0 a0  !  1 1 r r ra2a0 u1, 0 (r) p 1 e 2 a0 a0 2a0 4     5  2 2 r 2 r 2 r ra3a0 e u2, 0 (r) p 1 3 a0 27 a0 a0 3 3a0 4      3 5  1 3 r 1 r 2 1 r r ra4a0 e u3, 0 (r) p 1 4 a0 4 a0 8 a0 192 a0 a0  2 1 r u0, 1 (r) p era2a0 2 6a0 a0 4  5 2 8 1 r r u1, 1 (r) p 1 era3a0 6 a0 a0 27 6a0 s4     5 2 1 5 1 r 1 r 2 r u2, 1 (r) era4a0 1 16 3a0 4 a0 80 a0 a0  3 4 r era3a0 u0, 2 (r) p 81 30a0 a0  ! 3 1 1 r r u1, 2 (r) p 1 era4a0 12 a0 a0 64 5a0

9.3

Sizes and Shapes

191

1
1s radial eigenfunction

1
2p radial eigenfunction

0.5

0.5

0
0.5

10

0
0.5

10

2s radial eigenfunction

3p radial eigenfunction

0.5
0.5

10

15

20

0.5
0.5

10

15

20

3s radial eigenfunction

4p radial eigenfunction

0.5

10 20 30 D istance in Bohr radii

40

0.5

10 20 30 D istance in Bohr radii

40

Fig. 9.4 Radial eigenfunctions unr , l (r) for an electron in the hydrogen atom with radial quantum numbers nr 0, 1, and 2 and with angular momentum quantum numbers l 0 and 1. The eigenfunctions have been labelled using spectroscopic notation ns and np, where n is the principal quantum number n nr 1 l and s denotes l 0 and p denotes l 1. Note that the unit of distance is the Bohr radius a0 and that different scales are used for eigenfunctions with different values of nr .

9.3

SIZES AND SHAPES

The size and shape of a quantum state of atomic hydrogen can be determined by considering the most probable locations of the electron in the atom. For a state with eigenfunction cnr , l , ml (r, y, f), the probability of finding the electron with coordinates (r, y, f) in a volume element d3 r is jcnr , l , ml (r, y, f)j2 d3 rX We can easily find the radial probability distribution for the electron. To do so, we use d3 r r2 dr dV, where dV sin y dy df is an element of solid angle, and express the eigenfunction as